EP0172298B1 - Method for making thioether(bisphthalimide)s - Google Patents
Method for making thioether(bisphthalimide)s Download PDFInfo
- Publication number
- EP0172298B1 EP0172298B1 EP85100883A EP85100883A EP0172298B1 EP 0172298 B1 EP0172298 B1 EP 0172298B1 EP 85100883 A EP85100883 A EP 85100883A EP 85100883 A EP85100883 A EP 85100883A EP 0172298 B1 EP0172298 B1 EP 0172298B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methylphthalimide
- accordance
- sulfide
- bis
- hydrogen sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XARGIVYWQPXRTC-IENPIDJESA-N CCC1[C@@H](C)CCCC1 Chemical compound CCC1[C@@H](C)CCCC1 XARGIVYWQPXRTC-IENPIDJESA-N 0.000 description 1
- 0 C[C-]C(C1)C(C)CCC1Sc(cc1C)ccc1I*=C Chemical compound C[C-]C(C1)C(C)CCC1Sc(cc1C)ccc1I*=C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Definitions
- the present invention concerns a new method for synthesizing thioether(bisphthalimide)s which are useful as intermediates for making polytherimides and also as plasticizers, fire retardants, and antioxidants in organic polymers.
- the invention concerns a method of converting N-substituted halophthalimides and nithrophthalimides to thioether(bisphthalimide)s utilizing an alkali metal hydrogen sulfide (herein referred to as "MHS") instead of an alkali metal sulfide (M2S), where M is an alkali metal.
- MHS alkali metal hydrogen sulfide
- a method for synthesizing thioether(bisphthalimide)s from a reaction of an alkali metal sulfide and an N-substituted phthalmide has been accomplished and disclosed in U.S. Patent Number 4,054,584.
- the own prior filed EP 108 682 describes a method for making diarylthioethers which comprises heating a mixture of an anhydrous sulfide compound of the formula M2S and alkali metal hydrogen- sulfides of the formula MHS with N-substituted phthalimid compounds in the presence of a phase transfer catalyst.
- MHS alkali metal sulfide
- MHS 2H2O where M is an alkali metal
- M2S 9H2O where M is an alkali metal prior to their use in synthesizing thioether(bisphthalimide)s.
- the alkali metal hydrogen sulfides have improved solubility over alkali metal sulfides in organic solvents and therefore a smaller amount of solvent is required to facilitate reaction with phthalimides. This is particularly important since using dipolar aprotic solvents is costly.
- This improved solubility also permits higher yields to be obtained when using nonpolar solvents and a phase transfer catalyst than when utilising alkali metal sulfides.
- This process has produced yields of thioether(bisphthalimide)s of over 40 percent with nonpolar solvents (see example 5). This is important when attempting to avoid the use of the costly dipolar aprotic solvents.
- a product of the reaction process is H2S, which can be converted to the desired alkali metal hydrogen sulfide and recycled to the reaction process.
- thioether(bisphthalimide)s of the formula, where R is a monovalent radical selected from C (1-8) alkyl and C (6-20) aromatic hydrocarbon radicals. These compounds may be converted by a known process to the corresponding anhydrides of the formula, These thioether(bisphthalic anhydrides) of formula II may be employed as antioxidants in organic compounds, curing agents for epoxy resins, and as monomers in the formation of polyimides for high temperature use.
- alkali metal hydrogen sulfide acts as a base in removing hydrogen from the 4-n-methylphthalimide hydrogen sulfide initially formed producing an intermediate and H2S. This intermediate is then converted to thioether(bisphthalimide)s by combining with the 4-chloro-N-methylphthalimide present in the reaction mixture.
- the method for making the thioether(bisphthalimde)s of the formula comprises:
- the alkali metal hydrogen sulfide contains an alkali metal (M) such as sodium, potassium, lithium, etc.
- the alkali metal hydrogen sulfide may be in the hydrated form MHS 2H2O or in the anhydrous form.
- Sodium hydrogen sulfide (NaHS) is the preferred alkali metal sulfide used to produce the thioether(bispthalimide)s.
- N-substituted phthalimides are of the formula where X is either a nitro radical or a halo radical selected from fluoro, chloro, bromo and iodo; and R is a monovalent radical selected from C (1-8) alkyl radicals and C (6-20) aromatic radicals.
- radicals represented by R include, for example, methyl, ethyl, propyl, pentyl, octyl, isopropyl, etc.; and phenyl, tolyl, xylyl, naphthyl, chlorophenyl, bromotolyl, etc.
- N-substituted halophthalimides and nitrophthalimides of formula III include, for example, 4-chloro-N-methylphthalmide, 4-chloro-N-phenylphthalimide, 4-nitro-N-methylphthalimide, etc.
- the preferred N-substituted phthalimides are 4-chloro-N-methylphthalimide and 4-nitro-methylphthalimide, which produce high yields of bis(thioetherphthalimide) when employed in a reaction having a molar ratio 4-chloro-N-methylphthalimide to the alkali metal hydrogen sulfide of 2:1.
- the N-substituted phthalimide of formula III can be made by effecting reaction between substantially equal moles of organic amines, RNH2 (where R is as previously defined), and a substituted phthalic anhydride of the formula, where x has been previously defined. Included by RNH2 are organic amines such as aniline, toluidine, methylamine, ethylamine, etc.
- the dipolar aprotic solvents which can be utilized include, for example, dimethylformamide dimethylsulfoxide, dimethylacetamide, etc. Mixtures of such diplar aprotic solvents with nonpolar solvents such as, for example, toluene, chlorobenzene, dichlorobenzene, etc., may also be employed. These nonpolar solvents, such as toluene, may be used without a dipolar aprotic solvent if a phosphonium salt phase transfer catalyst is present.
- the preferred catalysts are of the formula P(R1)4+Br, where R1 is a monovalent radical selected from the group consisting of C (1-16) alkyl radicals and C (6-13) aromatic carbocyclic radicals.
- These catalysts include, for example, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and tetracyclohexylphosphonium bromide and tetracyclohexylphosphonium bromide, etc.
- Tetrabutylphosphonium bromide is the preferred catalyst where a nonpolar solvent is employed, which is preferably toluene.
- dipolar aprotic solvents such as, for example, dimethylformamide and dimethylacetamide, produces higher yields than nonpolar solvents since the formation of thioether(bisphthalimide)s is faster in dipolar aprotic solvents.
- the solution containing the alkali metal hydrogen sulfide and N-substituted phthalimide is maintained at a temperature in the range of 25°C to 150°c, and preferably in the range of 70°C to 150°C for a period ranging from 2 to 24 hours or more, depending upon the temperature, solvent utilized, the degree of agitation, ingredients used, etc.
- the thioether(bisphthalimide) product is recovered from the resulting mixture by a precipitation process. Adding water to the reaction mixture is the preferred method to cause the product to precipitate from the solution. Cooling the reaction mixture is an alternative method. The precipitate is filtered, dried, and recrystallized from an organic solvent, such as a 90:10 weight mixture of dichlorobenzene and heptane respectively.
- thioether(bisphthalimide)s that are produced are, for example, 3,3'-bis(N-methylphthalimide) sulfide, 4,4'-bis(N-methylphthalimide) sulfide; 3,3'-bis(N-phenylphthalimide) sulfide; 4,4'-bis(N-phenylphthalimide)sulfide; 3,3'-bis(n-butylphthalimide) sulfide; 4,4'-bis(N-butylphthalimide)sulfide; 3,4-bis(phenylphthalimide)sulfide, etc.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Description
- The present invention concerns a new method for synthesizing thioether(bisphthalimide)s which are useful as intermediates for making polytherimides and also as plasticizers, fire retardants, and antioxidants in organic polymers. The invention concerns a method of converting N-substituted halophthalimides and nithrophthalimides to thioether(bisphthalimide)s utilizing an alkali metal hydrogen sulfide (herein referred to as "MHS") instead of an alkali metal sulfide (M₂S), where M is an alkali metal.
- This method was discovered when attempts were made to prepare 4-N-methylphthalimide hydrogen sulfide. Surprisingly, the predominant product was 4,4'bis(N-methylphthalimide) from the reaction of a 1:1 mole ratio of sodium hydrogen sulfide to 4-chloro-N-methylphthalimide.
- A method for synthesizing thioether(bisphthalimide)s from a reaction of an alkali metal sulfide and an N-substituted phthalmide has been accomplished and disclosed in U.S. Patent Number 4,054,584.
- The own prior filed EP 108 682 describes a method for making diarylthioethers which comprises heating a mixture of an anhydrous sulfide compound of the formula M₂S and alkali metal hydrogen- sulfides of the formula MHS with N-substituted phthalimid compounds in the presence of a phase transfer catalyst.
- Starting from this state of the art it was found that utilizing MHS has advantages over the use of an alkali metal sulfide such as the ease of drying the hydrated form of MHS (MHS 2H₂O where M is an alkali metal) as compared to drying the hydrated form of an alkali metal sulfide (M₂S 9H₂O, where M is an alkali metal prior to their use in synthesizing thioether(bisphthalimide)s. Also, the alkali metal hydrogen sulfides have improved solubility over alkali metal sulfides in organic solvents and therefore a smaller amount of solvent is required to facilitate reaction with phthalimides. This is particularly important since using dipolar aprotic solvents is costly. This improved solubility also permits higher yields to be obtained when using nonpolar solvents and a phase transfer catalyst than when utilising alkali metal sulfides. This process has produced yields of thioether(bisphthalimide)s of over 40 percent with nonpolar solvents (see example 5). This is important when attempting to avoid the use of the costly dipolar aprotic solvents. In addition, a product of the reaction process is H₂S, which can be converted to the desired alkali metal hydrogen sulfide and recycled to the reaction process.
- Included among the compounds provided by the method of the present invention are thioether(bisphthalimide)s of the formula,
where R is a monovalent radical selected from C(1-8) alkyl and C(6-20) aromatic hydrocarbon radicals. These compounds may be converted by a known process to the corresponding anhydrides of the formula,
These thioether(bisphthalic anhydrides) of formula II may be employed as antioxidants in organic compounds, curing agents for epoxy resins, and as monomers in the formation of polyimides for high temperature use. -
- It is further believed that the alkali metal hydrogen sulfide acts as a base in removing hydrogen from the 4-n-methylphthalimide hydrogen sulfide initially formed producing an intermediate and H₂S. This intermediate is then converted to thioether(bisphthalimide)s by combining with the 4-chloro-N-methylphthalimide present in the reaction mixture.
-
- a) heating at 25°C to 150°C an anhydrous mixture comprising N-substituted phthalimide of the formula,
- b) precipitating the thioether(bisphthalimide) product from said mixture:
- The presence of the base such as triethylamine or tributylamine increases the yield of thioether(bisphthalimide)s.
- The alkali metal hydrogen sulfide (MHS) contains an alkali metal (M) such as sodium, potassium, lithium, etc. The alkali metal hydrogen sulfide may be in the hydrated form MHS 2H₂O or in the anhydrous form. Sodium hydrogen sulfide (NaHS) is the preferred alkali metal sulfide used to produce the thioether(bispthalimide)s.
- The N-substituted phthalimides are of the formula
where X is either a nitro radical or a halo radical selected from fluoro, chloro, bromo and iodo; and R is a monovalent radical selected from C(1-8) alkyl radicals and C(6-20) aromatic radicals. Examples of radicals represented by R include, for example, methyl, ethyl, propyl, pentyl, octyl, isopropyl, etc.; and phenyl, tolyl, xylyl, naphthyl, chlorophenyl, bromotolyl, etc. - Some of the N-substituted halophthalimides and nitrophthalimides of formula III include, for example, 4-chloro-N-methylphthalmide, 4-chloro-N-phenylphthalimide, 4-nitro-N-methylphthalimide, etc. The preferred N-substituted phthalimides are 4-chloro-N-methylphthalimide and 4-nitro-methylphthalimide, which produce high yields of bis(thioetherphthalimide) when employed in a reaction having a molar ratio 4-chloro-N-methylphthalimide to the alkali metal hydrogen sulfide of 2:1.
- The N-substituted phthalimide of formula III can be made by effecting reaction between substantially equal moles of organic amines, RNH₂ (where R is as previously defined), and a substituted phthalic anhydride of the formula,
where x has been previously defined. Included by RNH₂ are organic amines such as aniline, toluidine, methylamine, ethylamine, etc. - The dipolar aprotic solvents which can be utilized include, for example, dimethylformamide dimethylsulfoxide, dimethylacetamide, etc. Mixtures of such diplar aprotic solvents with nonpolar solvents such as, for example, toluene, chlorobenzene, dichlorobenzene, etc., may also be employed. These nonpolar solvents, such as toluene, may be used without a dipolar aprotic solvent if a phosphonium salt phase transfer catalyst is present. The preferred catalysts are of the formula P(R¹)₄⁺Br, where R¹ is a monovalent radical selected from the group consisting of C(1-16) alkyl radicals and C(6-13) aromatic carbocyclic radicals. These catalysts include, for example, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and tetracyclohexylphosphonium bromide and tetracyclohexylphosphonium bromide, etc. Tetrabutylphosphonium bromide is the preferred catalyst where a nonpolar solvent is employed, which is preferably toluene. However, the use of dipolar aprotic solvents such as, for example, dimethylformamide and dimethylacetamide, produces higher yields than nonpolar solvents since the formation of thioether(bisphthalimide)s is faster in dipolar aprotic solvents.
- To effect the reaction, the solution containing the alkali metal hydrogen sulfide and N-substituted phthalimide is maintained at a temperature in the range of 25°C to 150°c, and preferably in the range of 70°C to 150°C for a period ranging from 2 to 24 hours or more, depending upon the temperature, solvent utilized, the degree of agitation, ingredients used, etc.
- The thioether(bisphthalimide) product is recovered from the resulting mixture by a precipitation process. Adding water to the reaction mixture is the preferred method to cause the product to precipitate from the solution. Cooling the reaction mixture is an alternative method. The precipitate is filtered, dried, and recrystallized from an organic solvent, such as a 90:10 weight mixture of dichlorobenzene and heptane respectively.
- Some of the thioether(bisphthalimide)s that are produced are, for example, 3,3'-bis(N-methylphthalimide) sulfide, 4,4'-bis(N-methylphthalimide) sulfide; 3,3'-bis(N-phenylphthalimide) sulfide; 4,4'-bis(N-phenylphthalimide)sulfide; 3,3'-bis(n-butylphthalimide) sulfide; 4,4'-bis(N-butylphthalimide)sulfide; 3,4-bis(phenylphthalimide)sulfide, etc.
- In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
- To dry dimethylformamide (30 ml) here added 4-chloro-N-methylphthalimide (1.0g, 0.0051 mol), sodium hydrogen sulfide (0.14g, 0.0025 mol), biphenyl (0.20g, 0.0013 mol) and triethylamine (0.4 ml, 0.0025 mol). The solution was heated to 145°C for 12 hours. A sample of the reaction mixture was added to a dimethylformamide solution containing ethyl bromide and examined by high pressure liquid chromatography (HPLC) which indicated an 84% yield of 4,4'-bis(N-methylphthalimide)sulfide. The remaining reaction mixture was then added to water, the formed precipitate collected, dried, and recrystallized from a 90:10 weight mixture of o-dichlorobenzene and heptane. An isolated purified yield of 80% product (0.72g) was obtained, which had a melting point of 239°C.
- To a reaction vessel containing dimethylacetamide (25 ml) were added 4-nitro-N-methylphthalimide (0.50g, 0.00243 mol), biphenyl (0.204g, 0.00132 mol) and sodium hydrogen sulfide (0.14g, 0.0025 mol). The reaction was allowed to proceed at 70°C for 24 hours. samples of the reaction mixture were taken and examined by HPLC methods. A yield of 16.3% 4,4'bis(N-methylphthalimide)sulfide was indicated. The isolated yield was 15% (0.035g).
- The following were added to a reaction vessel: 4-chloro-N-methylphthalimide (0.53g, 0.0027 mol), sodium hydrogen sulfide (0.07g, 0.00125 mol), triethylamine (0.2 ml, 0.0014 mol), tetrabutylphosphonium bromide (0.15g, 0.00044 mol) and dry toluene (40 ml). The reaction was allowed to proceed at reflux (approximately 145°C) for 18 hours. The reaction mixture was sampled and tested by HPLC, which indicated a yield of 4,4'-bis(N-methylphthalimide) sulfide of 48.2%. The isolated yield was 45% (0.21g).
- To a reaction vessel were added 4-nitro-N-methylphthalimide (0.51g, 0. 00248 mol), sodium hydrogen sulfide (0.07g, 0.00125 mol), biphenyl (0.204g, 0.00132 mol), triethylamine (0.2 ml, 0.0014 mol), tetrabutylphosphonium bromide (0.15g, 0.00044 mol) and dry toluene (40 ml). The reaction mixture was allowed to proceed at reflux (approximately 145°C) for 18 hours. The reaction mixture was sampled and tested by HPLC which indicated a yield of 4,4'-bis(N-methylphthalimide)sulfide of 10% (0.04g).
- This example was run to investigate the mechanism of the reaction between the alkali metal hydrogen sulfides and the N-substituted halophthalimides.
- To dimethylformamide (30 ml) were added 4-chloro-N-methylphthalimide (0.0986g, 0.0051 mol), sodium hydrogen sulfide (0.15g, 0.00125 mol). The reaction mixture was heated to 120°C for 18 hours. A sample of the reaction mixture was recovered and examined by HPLC. A 35% yield (0.31g) of thioether(bis N-methylphthalimide) was obtained and a 50% yield (0.25g) of the intermediate 4-N-methylphthalimide hydrogen sulfide was obtained.
- It should be understood that the above examples represent only a limited number of bisimide sulfides of formula I which can be made in accordance with the practice of the invention.
wherein R is a monovalent radical selected from the group consisting of C(1-8) alkyl radicals and C(6-20) aromatic radicals, R' is selected from a group consisting of C(1-6) alkyl radicals and C(6-13) aromatic carbocyclic radicals, M is an alkali metal and X is a nitro radical or a halogen radical.
Claims (15)
- A method of making thioether(bisphthalimide)s of the formulaa) heating at 25°C to 150°C an anhydrous mixture comprising N-substituted phthalimide of the formula,b) precipitating the thioether(bisphthalimide) product from said mixture:wherein R is a monovalent radical selected from the group consisting of C(1-8) alkyl radicals and C(6-20) aromatic radicals, R' is selected from a group consisting of C(1-6) alkyl radicals and C(6-13) aromatic carbocyclic radicals, M is an alkali metal and X is a nitro radical or a halogen radical.
- A method in accordance with claim 1 where an organic base is present in said mixture.
- A method in accordance with claim 2 where the organic base is triethylamine.
- A method in accordance with claim 1 where the thioether(bisphthalimide) product is precipitated by the addition of water.
- A method in accordance with claim 1 where the alkali metal hydrogen sulfide is sodium hydrogen sulfide.
- A method in accordance with claim 1 where the N-substituted phthalimide is 4-chloro-N-methylphthalimide.
- A method in accordance with Claim 1 where said substituted phthalimide is 4-nitro-N-methylphthalimide.
- A method in accordance with claim 1 where said dipolar aprotic solvent utilized is selected from the group consisting of dimethylformamide and dimethylacetamide.
- A method in accordance with claim 1 where said nonpolar solvent utilized is toluene.
- A method in accordance with claim 1 where said phosphonium salt phase transfer catalyst is tetrabutylphosphonium bromide.
- A method in accordance with claim 5 where the molar ratio of 4-chloro-N-methylphthalimide to the alkali metal hydrogen sulfide is 2: 1.
- A method in accordance with claim 1 where said mixture is heated to a temperature in the range of 70°C to 150°C.
- A method of making 4,4'-bis(N-methylphthalimide)sulfide having the formula,a) heating at 25°C to 150°C an anhydrous mixture of 4-chloro-(N-methylphthalimide) and sodium hydrogen sulfide in the presence of dimethylformamide and triethylamine andb) precipitating 4,4'-bis(N-methylphthalimide sulfide).
- A method of making 4,4-bis(N-methylphthalimide) sulfide having the formula,a) heating at 25°C to 150°C an anhydrous mixture of 4 chloro(N-methylphthalimide) and sodium hydrogen sulfide in the presence of toluene, triethylamine and an effective amount of tetrabutylphosphonium bromide andb) precipitating the 4,4'-bis(N-methylphthalimide) sulfide.
- A method of making 4,4-bis(N-methylphthalimide) sulfide having the formula:a) heating at 25°C to 150°C an anhydrous mixture of 4-Nitro-(N-methylphthalimide) and sodium hydrogen sulfide in the presence of dimethylformamide and triethylamine;b) precipitating 4,4'-bis(N-methylphthalimide) sulfide.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/576,224 US4625037A (en) | 1984-02-02 | 1984-02-02 | Method for making thioether(bisphthalimide)s |
US576224 | 1984-02-02 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0172298A2 EP0172298A2 (en) | 1986-02-26 |
EP0172298A3 EP0172298A3 (en) | 1988-01-13 |
EP0172298B1 true EP0172298B1 (en) | 1991-09-11 |
Family
ID=24303467
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85100883A Expired EP0172298B1 (en) | 1984-02-02 | 1985-01-29 | Method for making thioether(bisphthalimide)s |
Country Status (4)
Country | Link |
---|---|
US (1) | US4625037A (en) |
EP (1) | EP0172298B1 (en) |
JP (1) | JPS60188368A (en) |
DE (1) | DE3584056D1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4866184A (en) * | 1986-10-10 | 1989-09-12 | Ethyl Corporation | Producing bis(alicyclic) thioethers |
US4757149A (en) * | 1986-12-31 | 1988-07-12 | General Electric Company | Synthesis of bis(N-substituted phthalimide)ethers |
CA1299801C (en) * | 1987-03-31 | 1992-04-28 | Chung J. Lee | Soluble polyimidesiloxanes and methods for their preparation and use |
US4870194A (en) * | 1987-09-28 | 1989-09-26 | Occidental Chemical Corporation | Process for the preparation and recovery of oxdiphthalic anhydrides |
US5077415A (en) * | 1990-01-19 | 1991-12-31 | Ciba-Geigy Corporation | Disubstituted aromatic dianhydrides |
JP2011506691A (en) | 2007-12-19 | 2011-03-03 | 中国科学院▲寧▼波材料技▲術▼▲与▼工程研究所 | Polythioetherimide and process for producing the same |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3989712A (en) * | 1973-03-30 | 1976-11-02 | General Electric Company | Thio-bis(phthalimides) |
US4054584A (en) * | 1973-03-30 | 1977-10-18 | General Electric Company | Method for making bis(thioether anhydride)s |
FR2277834A1 (en) * | 1974-07-12 | 1976-02-06 | Gen Electric | Bis-(thioether-phthalimides and-anhydrides - useful as antioxidants, epoxy resin curing agents, and inters for polyester resins |
US4102905A (en) * | 1977-09-02 | 1978-07-25 | General Electric Company | Aromatic disulfone dianhydrides |
JPS55122757A (en) * | 1979-03-14 | 1980-09-20 | Mitsui Toatsu Chem Inc | Production of thio-di-phthalic acid or anhydride |
US4273712A (en) * | 1979-05-09 | 1981-06-16 | General Electric Company | Method for making aromatic ether imides |
US4499285A (en) * | 1982-11-01 | 1985-02-12 | General Electric Company | Solvent free preparation of diarylthioethers |
US4476309A (en) * | 1983-03-21 | 1984-10-09 | General Electric Company | Method for making aromatic etherimides |
-
1984
- 1984-02-02 US US06/576,224 patent/US4625037A/en not_active Expired - Lifetime
-
1985
- 1985-01-29 EP EP85100883A patent/EP0172298B1/en not_active Expired
- 1985-01-29 DE DE8585100883T patent/DE3584056D1/en not_active Expired - Fee Related
- 1985-01-30 JP JP60014587A patent/JPS60188368A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0172298A3 (en) | 1988-01-13 |
JPS60188368A (en) | 1985-09-25 |
EP0172298A2 (en) | 1986-02-26 |
US4625037A (en) | 1986-11-25 |
DE3584056D1 (en) | 1991-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4273712A (en) | Method for making aromatic ether imides | |
US4257953A (en) | Method for making bisphenoxide salts and bisimides derived therefrom | |
CA1095917A (en) | Method for making organic polycarboxylic acids | |
US5081298A (en) | Bis(pentaalkylguanidinium) alkane salts as phase transfer catalysts | |
JPS6220185B2 (en) | ||
US4329496A (en) | Method for making aromatic bis(ether phthalic acid) or aromatic bis(ether anhydride) | |
US5068353A (en) | Synthesis of aromatic bis(ether phthalimide) compounds | |
US4808731A (en) | Method for making oxydiphthalic anhydride | |
EP0172298B1 (en) | Method for making thioether(bisphthalimide)s | |
US4769493A (en) | Process for producing tetrafluorophthalic acid | |
JPS604134A (en) | Manufacture of aromatic ethers and catalyst therefor | |
US4302616A (en) | Method for making alkali metal bisphenoxide salts and bisimides derived therefrom | |
US4933469A (en) | Method for preparing oxybisphthalimides | |
CA1207329A (en) | Solvent free preparation of diarylthioethers | |
EP0250981B1 (en) | Method for making bisimides | |
US4757149A (en) | Synthesis of bis(N-substituted phthalimide)ethers | |
US3989712A (en) | Thio-bis(phthalimides) | |
JPS58180479A (en) | Manufacture of aromatic bis(ether acid anhydride) | |
US4467097A (en) | Method for making aromatic bis(etherimide)s | |
KR940000062B1 (en) | Process for preparation of acylcyanide in medium anhydride | |
JPS5949217B2 (en) | Method for producing substituted diphenyl ether | |
US5208346A (en) | Simplified process for the preparation of aromatic bismides | |
EP0259663A1 (en) | Process for producing tetrafluorophihalic acid | |
JPS6160647A (en) | Preparation of n-substituted monomaleimide | |
KR950008208B1 (en) | Method for preparation of mercaptobenzoates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19880708 |
|
17Q | First examination report despatched |
Effective date: 19900629 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REF | Corresponds to: |
Ref document number: 3584056 Country of ref document: DE Date of ref document: 19911017 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19911206 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19911230 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19920131 Year of fee payment: 8 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19921001 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19930129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930801 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19930129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19930930 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |